An NBO analysis of the electron distribution in the DFT-optimized geometries of different Cp2TiIV(L,L'-BID) complexes with L,L'-BID = dioxolene, dithiolene or diselenolene, showed that a large degree of folding along the L...L axis is needed for sufficient Ti←L π-donation. The out of plane folding for maximum Ti←L π donation increases with larger Ti-L bond lengths: Cp2TiIV(O,O'-BID) (~35 °) < Cp2TiIV(S,S'-BID) (47 ° average) < Cp2TiIV(Se,Se'-BID) (50 ° average).